Compositions of Corrosion-resistant Fe-Based Amorphous Metals Suitable for Producing Thermal Spray Coatings

ABSTRACT

A method of coating a surface comprising providing a source of amorphous metal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron; and applying said amorphous metal to the surface by a spray.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of application Ser. No. 11/595,166filed Nov. 9, 2006, entitled “Compositions of Corrosion-ResistantFe-Based Amorphous Metals Suitable for Producing Thermal SprayCoatings”. This application claims the benefit of U.S. ProvisionalPatent Application No. 60/737,029, filed Nov. 14, 2005, and titled“High-Performance Corrosion Resistant Material: New Compositions ofCorrosion-Resistant Fe-Based Amorphous Metals Suitable for ProducingThermal Spray Coatings”, which are incorporated herein by thisreference.

STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSOREDRESEARCH AND DEVELOPMENT

The United States Government has rights in this invention pursuant toContract No. DE-AC52-07NA27344 between the United States Department ofEnergy and Lawrence Livermore National Security, LLC for the operationof Lawrence Livermore National Laboratory.

BACKGROUND

1Field of Endeavor

The present invention relates to corrosion and more particularly tocorrosion resistant material.

2. State of Technology

U.S. Pat. No. 6,258,185 issued Jul. 10, 2001 to Daniel Branagan andJoseph V. Burch for methods of forming steel provides the followingstate of technology information:

“4. A method of forming a steel, comprising: forming a molten alloy;cooling the alloy at a rate which forms a metallic glass; devitrifyingthe metallic glass to convert the glass to a crystalline steel materialhaving a nanocrystalline scale grain size; and transforming a portion ofthe crystalline steel material to metallic glass.

8. The method of claim 4 wherein the molten alloy comprises: at least50% Fe; at least one element selected from the group consisting of Ti,Zr, HF, V, Nb, Ta, Cr, Mo, W, Al, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy,Ho, Er, Tm, Yb, and Lu; and at least one element selected from the groupconsisting of B, C, N, O, P and S.

9. The method of claim 4 wherein the molten alloy comprises a materialselected from the group consisting of Fe₆₉Zr₃Mo₇P₁₆C₃Si₂,Fe₇₁Ti₃Cr₇B₁₄C₃Si₂, Fe₆₈Cr₄Mo₇P₁₂B₆C₃, DNA3, DNS2C, and DNA6.

14. A method of forming a steel, comprising: providing a first metallicglass steel substrate; forming a molten alloy over the first metallicglass steel substrate to heat and devitrify at least some of theunderlying metallic glass of the steel substrate.

18. The method of claim 14 wherein the molten alloy comprises a materialselected from the group consisting of Fe₆₉Zr₃Mo₇P₁₆C₃Si₂,Fe₇₁Ti₃Cr₇B₁₄C₃Si₂, Fe₆₈Cr₄Mo₇P₁₂B₆C₃, DNA3, DNS2C and DNA6.

19. The method of claim 14 wherein the first metallic glass substratecomprises a material selected from the group consisting ofFe₆₉Zr₃Mo₇P₁₆C₃Si₂, Fe₇₁Ti₃Cr₇B₁₄C₃Si₂, Fe₆₈Cr₄Mo₇P₁₂B₆C₃, DNA3, DNS2Cand DNA6.” (Claims 4, 8, 9, 14, 18, and 19)

U.S. Pat. No. 6,767,419 issued Jul. 27, 2004 to Daniel Branagan formethods of forming hardened surfaces provides the following state oftechnology information: “A method of forming a hardened surface on asubstrate, comprising: providing a substrate; forming a molten alloy andcooling said alloy to form a metallic glass coating on the substrate;the forming comprising a successive build-up of metallic glass layers,the metallic glass comprising one or more materials selected from thegroup consisting of (Fe_(0.85)Cr_(0.15))₈₃B₁₇, (Fe_(0.8)Cr_(0.2))₈₃B₁₇,(Fe_(0.75)C_(0.25))₈₃B_(17,) (Fe_(0.6)Co_(0.2)Cr0.2)₈₃B₁₇,(Fe_(0.8)Cr_(0.15)Mo_(0.05))₈₃B₁₇, (Fe_(0.8)Cr_(0.2))₇₉B₁₇C₄,(Fe_(0.8)Cr_(0.2))₇₉B₁₇Si₄, (Fe_(0.8)Cr_(0.2))₇₉B₁₇Al₄,(Fe_(0.8)Cr_(0.2))₇₅B₁₇Al₄C₄, (Fe_(0.8)Cr_(0.2))₇₅B₁₇Si₄C₄,(Fe_(0.8)Cr_(0.2))₇₅B₁₇Si₄Al₄, (Fe_(0.8)Cr_(0.2))₇₁B₁₇Si₄C₄Al₄,(Fe_(0.7)Co_(0.1)Cr_(0.2))₈₃B₁₇, (Fe_(0.8)Cr_(0.2))₈₀B₂₀,(Fe_(0.8)Cr_(0.2))₇₆B₁₇Al₇, (Fe_(0.8)Cr_(0.2))₇₉B₁₇W₂C₂,(Fe_(0.8)Cr_(0.2))₈₁B₁₇W₂, and Fe 64 Ti 3 Cr 5 Mo₂B₁₆C₅Si₁Al₂La₂; themetallic glass coating having a hardness of at least about 9.2 GPa andconverting at least a portion of the metallic glass coating to acrystalline material having a nanocrystalline grain size.” (Claim 13)

United States Patent Application No. 2003/0051781 by Daniel J. Branaganfor hard metallic materials, hard metallic coatings, methods ofprocessing metallic materials and methods of producing metalliccoatings, published Mar. 20, 2003 provides the following state oftechnology information: “Both microcrystalline grain internal structuresand metallic glass internal structures can have properties which aredesirable in particular applications for steel. In some applications,the amorphous character of metallic glass can provide desiredproperties. For instance, some glasses can have exceptionally highstrength and hardness. In other applications, the particular propertiesof microcrystalline grain structures are preferred. Frequently, if theproperties of a grain structure are preferred, such properties will beimproved by decreasing the grain size. For instance, desired propertiesof microcrystalline grains (i.e., grains having a size on the order of10⁻⁶ meters) can frequently be improved by reducing the grain size tothat of nanocrystalline grains (i.e., grains having a size on the orderof 10⁻⁹ meters). It is generally more problematic, and not generallypossible utilizing conventional approaches, to form grains ofnanocrystalline grain size than it is to form grains of microcrystallinegrain size.”

United States Patent Application No. 2005/0013723 for formation ofmetallic thermal barrier alloys by Daniel James Branagan published Jan.20, 2005 provides the following state of technology information: “Metalsand metallic alloys have metallic bonds consisting of metal ion coressurrounded by a sea of electrons. These free electrons which arise froman unfilled outer energy band allow the metal to have high electricaland thermal conductivity which makes this class of materials conductors.Due to the nature of the metallic bonds, metals and metallic alloys mayexhibit a characteristic range of properties such as electrical andthermal conductivity. Typical metallic materials may exhibit values ofelectrical resistivity that generally fall in a range of between about1.5 to 145 10 ⁻⁸ Ωm, with iron having an electrical resistivity of about8.6 10⁻⁸ Ωm. Typical values of thermal conductivity for metallicmaterials may be in a range of between about 0.2 to 4.3 watts/cm° C.,with iron exhibiting a thermal conductivity of about 0.8 watts/cm° C.(Paragraph [0003]) By contrast, ceramics are a class of materials whichtypically contain positive ions and negative ions resulting fromelectron transfer from a cation atom to an anion atom. All of theelectron density in ceramics is strongly bonded resulting in a filledouter energy band. Ceramic alloys, due to the nature of their ionicbonding, will exhibit a different characteristic range of propertiessuch as electrical and thermal conductivity. Because of the lack of freeelectrons, ceramics generally have poor electrical and thermalconductivity and are considered insulators. Thus, ceramics may besuitable for use in applications such as thermal barrier coatings whilemetals are not. (Paragraph [0004]) Designing a metal alloy to exhibitceramic like electrical and thermal conductivities is unique. The onlyarea where this has been utilized in material science is in the designof soft magnetic materials for transformer core applications. In suchapplications, extra silicon is added to iron in order to specificallyreduce the electrical conductivity to minimize eddy current losses.However, iron-silicon alloys utilized for transformer cores typicallycontain a maximum of 2.5 at % (atomic percent) silicon because anyadditional silicon embrittles the alloy. Additionally, attempts toreduce electrical conductivity of iron transformer cores have notaddressed reduced thermal conductivity.” (Paragraph [0005])

SUMMARY

Features and advantages of the present invention will become apparentfrom the following description. Applicants are providing thisdescription, which includes drawings and examples of specificembodiments, to give a broad representation of the invention. Variouschanges and modifications within the spirit and scope of the inventionwill become apparent to those skilled in the art from this descriptionand by practice of the invention. The scope of the invention is notintended to be limited to the particular forms disclosed and theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

The present invention provides a method of coating a surface comprisingproviding a source of amorphous metal that contains manganese (1 to 3atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic%) in the range of composition given in parentheses; and that containsthe following elements in the specified range of composition given inparentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic%), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to16 atomic %), and the balance iron; and applying said amorphous metal tothe surface by a spray. In other embodiments the specific ranges are thefollowing: manganese (1.5 to 2.9 atomic %), yttrium (0.1 to 7 atomic %),and silicon (0.3 to 3.1 atomic %) in the range of composition given inparentheses; and that contains the following elements in the specifiedrange of composition given in parentheses: chromium (14.6 to 19.2 atomic%), molybdenum (2.3 to 14 atomic %), tungsten (1.4 to 3 atomic %), boron(5.9 to 16 atomic %), carbon (3.7 to 15 atomic %), and (iron 41-76atomic %). The present invention also provides a coating made of theamorphous metal. Table 1 below provides additional information.

TABLE 1 Ranges of Composition Ranges Based on HPCRM Research SAM40SAM2X5 SAM1651 Element Atomic Percent (at. %) Fe 43-59 52.3 49.7 48.0 Ni1-7 Co Mn 1-2 2.0 1.9 Cr 14-22 19.0 18.1 15.0 Mo  2-16 2.5 7.4 14.0 W1-3 1.7 1.6 B  5-17 16.0 15.2 6.0 C  3-15 4.0 3.8 15.0 P 10 Si 1-5 2.52.4 Al Zr 1-7 Ti 1-7 Nb Ta Y 1-7 2.0 Er

The present invention has use as a coating for naval ships andsubmarines; containers for shipment, storage and disposal of spentnuclear fuel; pressurized water and boiling water nuclear reactors;breeder reactors with liquid metal coolant; nuclear power systems;fossil energy power plants; chemical plants; bridges; structures; andmarine applications, and other applications.

The invention is susceptible to modifications and alternative forms.Specific embodiments are shown by way of example. It is to be understoodthat the invention is not limited to the particular forms disclosed. Theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated into and constitute apart of the specification, illustrate specific embodiments of theinvention and, together with the general description of the inventiongiven above, and the detailed description of the specific embodiments,serve to explain the principles of the invention.

FIG. 1 illustrates one embodiment of a system of the present invention.

FIG. 2 illustrates another embodiment of a system of the presentinvention.

FIG. 3 illustrates yet another embodiment of a system of the presentinvention.

FIG. 4 shows X-ray diffraction pattern for drop-cast ingot of SAM1651(LDAR7 OR CBCTL1651), that shows virtually no crystalline structure.Peak broadening of all three HVOF coatings suggest presence of some finecrystalline phase(s) in the amorphous matrix.

FIGS. 5A and 5B illustrate X-ray diffraction (XRD) that shows that thematrices of melt-spun ribbons of SAM40 (DAR40) parent material anddrop-cast ingots of SAM1651 (LDAR7 OR CBCTL1651) remain amorphous to500° C. However, XRD is not effective for detecting dispersedcrystalline phase(s) that account for less than 2 volume % of thematerial. Electron microscopy was used to compensate for thisshortcoming.

FIG. 6 shows a parametric study of the HVOF process was conducted withSAM40 (DAR40), with the mean particle size of the sprayed powder and thesubstrate temperature systematically varied. While coatings producedwith relatively large particles (>54 μm) showed un-melted andun-consolidated particles embedded in the coating, with substantialporosity and poor interfacial bonding, coatings produced with smallerparticles (20 to 23 μn) are essentially homogeneous, pore-free andwell-bonded.

FIGS. 7A, 7B, and 7C illustrates an X-ray diffraction SAM40 (DAR40)deposited with HVOF during a parametric study that shows the coatingsproduced with smaller particles (25 μm) are more glassy, with fewerresidual crystalline phases, than the coatings produced with largerparticles (38 to 53 μm).

FIG. 8 elemental mapping shows the formation of crystalline phases inmelt-spun ribbons of SAM40 (DAR40) after a 1-hour exposure at 800° C.Substantial crystallization occurs after a 1-hour exposure at 1000° C.

FIG. 9 elemental mapping shows no formation of crystalline phases inarc-melted drop-cast ingots of SAM1651 (LDAR7 OR CBCTL1651) after a1-hour exposure at 800° C., but the onset of crystallization after a1-hour exposure at 1000° C. Small yttrium oxide particles remainedunaffected in the matrix.

FIG. 10 shows a comparison of the original SAM40 (DAR40) formulation tothe SAM1651 (LDAR7 OR CBCTL1651) formulation, in regard to thermalstability at 800° C. and coating morphology.

FIGS. 11A and 11B predicted Pourbaix diagrams for SAM1651 (LDAR7 ORCBCTL1651) and SAM1651+W amorphous metal formulations in syntheticseawater at near-ambient temperature (30° C.). In the later case, thepresence of tungsten leads to the formation of FeWO₄ and WO₂(OH)₂, whilethe presence of molybdenum leads to the formation of MoO₂ and MO₃.Chromium and iron oxides (Cr₂O₃ and Fe₂O₃) also contribute to passivefilm stability. Under alkaline conditions, stable Y₂O₃ and NaO₄W surfacephases are predicted. Such predicted Pourbaix diagrams, and thecapability developed to make such predictions, is clear evidence thatMilestone 1 has been met.

FIGS. 12A and 12B predicted Pourbaix diagrams for SAM1651 amorphousmetal formulations in concentrated calcium chloride brines at 30 and 90°C. Under acidic-to-neutral conditions, MoO₂, MO₃, CaO-MO₃, Cr₂O₃ andFe₂O₃ contribute to passive film stability. Under alkaline conditions,stable Y₂O₃ and Ca(OH)₂ surface phases are also predicted.

FIGS. 13A and 13B predicted Pourbaix diagrams for SAM1651+W amorphousmetal formulations in concentrated calcium chloride brines at 105 and118° C. The presence of tungsten leads to the formation of FeWO₄ andWO₂(OH)₂, while the presence of molybdenum leads to the formation ofMoO₂, MO₃ and CaO-MO₃. Chromium and iron oxides (Cr2_(O) ₃ and Fe₂O₃)also contribute to passive film stability. Under alkaline conditions,stable Y₂O₃ and Ca(OH)₂ surface phases are predicted.

FIG. 14 is an actual cyclic polarization curve for Alloy C-22 in 5MCaCl₂ at 105° C., showing three methodologies for determining thethreshold potential for the initiation of localized corrosion inperformance assessment models. Method A is based upon the criticalpotential at which the passive film breaks down (current excursion, 2 or20 mA/cm²). Method B is based upon the repassivation potential, which inturn is based upon an arbitrary threshold (1 or 2 mA/cm2). Method C isbased upon the repassivation potential, determined from the intersectionof the hysteresis loop with the forward scan.

FIG. 15 shows the predicted role of chromium, molybdenum, tungsten andtitanium on passive film stability, based upon knowledge of the Pourbaixdiagrams of each of these alloying elements. This figure was based on anearlier figure prepared for presentation to the Nuclear Waste TechnicalReview Board, but without any specific reference to HVOF SAM. This wasan earlier prediction (cartoon depiction of the yet-to-be-measuredperformance of SAM2×5 (LDAR2×5) and SAM1651 (LDAR7 OR CBCTL1651).

FIGS. 16A and 16B show the benefits of Mo additions on the enhancementof Alloy C-22 corrosion resistance in comparison to that of Type 316Lstainless steel. This recognized beneficial effect of molybdenum hasbeen fully exploited in the enhancement and optimization of the earlyDAR-type compositions of NanoSteel, thereby rendering them far morecorrosion resistant than first observed.

FIG. 17 cyclic polarization of wrought nickel based Alloy C-22 (N06022)and iron-based amorphous metal (SAM1651) ingot in 5M CaCl₂ at 105° C.Alloy C-22 shows catastrophic breakdown of the passive film at 100 mVvs. Ag/AgCl, which causes a very large hysteresis loop. During thereverse scan, repassivation occurs at a relatively low potential (−150to −200 mV). While there was catastrophic breakdown of the Alloy C-22 atvery low potential (100 to 200 mV vs. Ag/AgCl), no breakdown of thepassive film on SAM1651 ingot was observed, even at potentialsapproaching that required for oxygen evolution.

FIG. 18 various alloy samples, ranked based upon their measuredresistance to localized corrosion (ΔE=E_(corr)−E_(rp)) in 5M CaCl2 at105° C. With the exception of the P-containing Fe-based amorphous metal(Pang et al.), most of the amorphous metals performed very well in thisaggressive environment. In contrast, the performance of the wroughtnickel-based Alloy C-22 (N06022) was relatively poor.

FIG. 19 comparison of the cyclic polarization curves for a SAM1651(LDAR7 OR CBCTL1651) amorphous metal ingot, a sample of wroughtnickel-based Alloy C-22, and a sample of thermally spray Alloy C-22 inambient temperature, Half Moon Bay seawater is shown. The SAM1651 (LDAR7OR CBCTL1651) amorphous metal had better corrosion resistance than bothwrought and HVOF Alloy C-22.

FIG. 20 various alloy samples, ranked based upon their measuredresistance to localized corrosion (ΔE=E_(corr)−E_(rp)) in Half Moon Bayseawater at 90° C. Most of the amorphous-samples performed very well,with the arc-melted drop-cast ingot of SAM1651 (LDAR7 OR CBCTL1651)showing the best performance. The electrochemical performance of thesematerials in seawater was as good as Alloy C-22, and superior to Type316L stainless steel.

FIG. 21 cyclic polarization curve is for a melt-spun ribbon of LDAR8 in5M CaCl2 at 105° C. The LDAR8 formulation uses SAM1651 (Y-containing,high-Mo Fe-based amorphous metal) as the parent material, with theaddition of tungsten at 3 atomic percent. The repassivation potentialfor LDAR8 in this aggressive environment (300-400 mV vs. Ag/AgCl) issubstantially higher than that for Alloy C-22 (−100 mV vs. Ag/AgCl).

FIGS. 22A, 22B, and 22C are early thermal-spray coatings of Type 316Lstainless steel and the SAM40 (DAR40) parent material showed relativelysevere corrosive attack after only 13 cycles in the ASTM B117 salt fogtest. However, several of the new Fe-based amorphous metal coatings,including SAM1651 (LDAR7 OR CBCTL1651) and SAM2×5 (LDAR2×5), have shownno corrosion, even after more than 30 cycles in this aggressiveenvironment. It is therefore believed that these new materials willprovide substantial benefit in some Naval applications.

FIGS. 22D, 22E, 22F, and 22G are early thermal-spray coatings of Type316L stainless steel and the SAM40 (DAR40) parent material showedrelatively severe corrosive attack after only 13 cycles in the ASTM B117salt fog test. However, several of the new Fe-based amorphous metalcoatings, including SAM1651 (LDAR7 OR CBCTL1651) and SAM2×5 (LDAR2×5),have shown no corrosion, even after more than 30 cycles in thisaggressive environment. It is therefore believed that these newmaterials will provide substantial benefit in some Naval applications.

DETAILED DESCRIPTION OF THE INVENTION

Referring to the drawings, to the following detailed description, and toincorporated materials, detailed information about the invention isprovided including the description of specific embodiments. The detaileddescription serves to explain the principles of the invention. Theinvention is susceptible to modifications and alternative forms. Theinvention is not limited to the particular forms disclosed. Theinvention covers all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theclaims.

The present invention provides a coating comprising a composite materialmade of amorphous metal that contains the following elements in thespecified range of composition given in parentheses: manganese (1 to 3atomic %), yttrium (0.1 to 10 atomic %), silicon (0.3 to 3.1 atomic %),chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), andthe balance iron. The present invention also provides a system forforming a coating comprising using a spray process to deposit theamorphous metal. The present invention utilizes combinatorial synthesismethodology based upon the marriage of statistical optimizationapproaches with computational thermodynamics and phase transformationkinetics. The present invention also provides coating processes that usecold-spray methodology to deposit mechanically hard, corrosion-resistantamorphous metals, using a softer corrosion-resistant metal or binder toenable this low-temperature coating process. Coating processes for thedeposition phosphorous-containing iron-based amorphous-metal coatingsthat rely on cold-spray methodology to overcome problems associated withthe thermal-spray of phosphorous containing materials (including thepossible generation of volatile, organo-phosphorous compounds). Thepresent invention provides a method of coating a surface comprisingproviding a source of amorphous metal that contains manganese (1 to 3atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic%) in the range of composition given in parentheses; and that containsthe following elements in the specified range of composition given inparentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic%), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to16 atomic %), and the balance iron; and applying said amorphous metal tothe surface by a spray.

Background information relating to the present invention is described inthe following publications: (1) United States Patent Application No.2003/0051781 by Daniel J. Branagan for hard metallic materials, hardmetallic coatings, methods of processing metallic materials and methodsof producing metallic coatings, published Mar. 20, 2003; (2) U.S. Pat.No. 6,767,419 issued Jul. 27, 2004 to Daniel Branagan for methods offorming hardened surfaces provides the following state of technologyinformation, and (3) United States Patent Application No. 2005/0013723for formation of metallic thermal barrier alloys by Daniel JamesBranagan published Jan. 20, 2005. United States Patent Application No.2003/0051781 by Daniel J. Branagan for hard metallic materials, hardmetallic coatings, methods of processing metallic materials and methodsof producing metallic coatings, published Mar. 20, 2003; U.S. Pat. No.6,767,419 issued Jul. 27, 2004 to Daniel Branagan for methods of forminghardened surfaces provides the following state of technologyinformation, and United States Patent Application No. 2005/0013723 forformation of metallic thermal barrier alloys by Daniel James Branaganpublished Jan. 20, 2005 are incorporated herein by reference.

Referring now to the drawings and in particular to FIG. 1, oneembodiment of a system of the present invention is illustrated. Thisembodiment is designated generally by the reference numeral 100. Theembodiment 100 provides a corrosion resistant amorphous metal coating101. The corrosion resistant amorphous metal coating 101 is produced byspray processing to form a coating made of amorphous metal. Asillustrated in FIG. 1, a corrosion-resistant amorphous-metal 102 issprayed to form the coating 101. The coating 101 is applied to thesurface 103 of a structure 104. The coating 101 is applied to thesurface 103 by the spray 102 using a spray device 105. The coating 101comprising a composite material made of amorphous metal that containsthe following elements in the specified range of composition given inparentheses: manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %),and silicon (0.3 to 3.1 atomic %) in the range of composition given inparentheses; and that contains the following elements in the specifiedrange of composition given in parentheses: chromium (15 to 20 atomic %),molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to16 atomic %), carbon (3 to 16 atomic %), and the balance iron.

The present invention has many uses. For example, the present inventioncan be used for metal-ceramic armor; projectiles; gun barrels, tankloader trays, rail guns, non-magnetic hulls, hatches, seals, propellers,rudders, planes, ships, submarine oil and water drilling equipment;earth moving equipment; tunnel-boring machinery; pump impellers &shafts; containers for shipment, storage and disposal of spent nuclearfuel; pressurized and boiling water nuclear reactors; breeder reactorswith liquid metal coolant, and other uses. Such materials could also beused to coat the entire outer surface of containers for thetransportation and long-term storage of high-level radioactive waste(HLW) spent nuclear fuel (SNF), or to protect welds and heat affectedzones, thereby preventing exposure to environments that might causestress corrosion cracking. In the future, it may be possible tosubstitute such high-performance iron-based materials for more-expensivenickel-based alloys, thereby enabling cost savings in various industrialapplications.

Referring now to FIG. 2, another embodiment of a system of the presentinvention is illustrated. This embodiment is designated generally by thereference numeral 200. The embodiment 200 provides a corrosion resistantamorphous metal coating 207. The corrosion resistant amorphous metalcoating 207 is produced by spray processing to form a composite coatingmade of amorphous metal. As illustrated in FIG. 2, the alternatinglayers 201, 202, 203, etc. of coating 207 are applied to a structure204. A spray device 206 produces the spray 205.

As illustrated in FIG. 2, a corrosion-resistant amorphous-metal issprayed to form the coating 207 containing a multiplicity of layers 201,202, 203, etc. Each of the coating layers 201, 202, 203 is made ofadvanced formulations of corrosion-resistant amorphous-metals. Forexample the coating layer 201 comprises a composite material made ofamorphous metal that contains the following elements in the specifiedrange of composition given in parentheses: manganese (1 to 3 atomic %),yttrium (0.1 to 10 atomic %), silicon (0.3 to 3.1 atomic %), chromium(15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and thebalance iron.

The present invention has many uses. For example, the present inventioncan be used for metal-ceramic armor; projectiles; gun barrels, tankloader trays, rail guns, non-magnetic hulls, hatches, seals, propellers,rudders, planes, ships, submarine oil and water drilling equipment;earth moving equipment; tunnel-boring machinery; pump impellers &shafts; containers for shipment, storage and disposal of spent nuclearfuel; pressurized and boiling water nuclear reactors; breeder reactorswith liquid metal coolant, and other uses. Such materials could also beused to coat the entire outer surface of containers for thetransportation and long-term storage of high-level radioactive waste(HLW) spent nuclear fuel (SNF), or to protect welds and heat affectedzones, thereby preventing exposure to environments that might causestress corrosion cracking. In the future, it may be possible tosubstitute such high-performance iron-based materials for more-expensivenickel-based alloys, thereby enabling cost savings in various industrialapplications.

Referring now to FIG. 3, another embodiment of a system of the presentinvention is illustrated. This embodiment is designated generally by thereference numeral 300. A deposition chamber 301 contains a depositionsystem including magnetron 302 and sputter target 303. The magnetron 302and sputter target 303 produce deposition spray 304. The depositionspray is directed onto the surface of the structure 305 that is to becoated. The deposition spray 304 forms the layers 306 and 307 onstructure 305. Each of the coating layers 306 and 307 are made ofadvanced formulations of corrosion-resistant amorphous-metals. Forexample the coating layers 306 and 307 each comprises a compositematerial made of amorphous metal that contains the following elements inthe specified range of composition given in parentheses: manganese (1 to3 atomic %), yttrium (0.1 to 10 atomic %), silicon (0.3 to 3.1 atomic%), chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %),tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16atomic %), and the balance iron.

The structure 305 can be an element of a plane, a ship, a submarine, oiland water drilling equipment, earth moving equipment, tunnel-boringmachinery, or other equipment. The element coated by the system 300 canbe used for metal armor, projectiles, gun barrels, tank loader trays,rail guns, non-magnetic hulls, hatches, seals, propellers, rudders, pumpimpellers and shafts, containers for spent nuclear fuel, pressurizedwater reactors, boiling water reactors, breeder reactors with liquidmetal coolant, and other uses. The element coated by the system 300 canbe used for containers for the transportation and long-term storage ofhigh-level radioactive waste (HLW) spent nuclear fuel (SNF), or toprotect welds and heat affected zones, thereby preventing exposure toenvironments that might cause stress corrosion cracking. Another use ofthe coating 308 is to substitute it for more-expensive nickel-basedalloys, thereby enabling cost savings in various industrialapplications.

The deposition units 302 that produce the deposition spray 303 anddeposition spray 304 are sources of amorphous metal that produce thecoating layers 306 and 307 on the structure 305. For example, the sourceof the deposition spray 303 can be a source of amorphous metal thatcontains manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), andsilicon (0.3 to 3.1 atomic %) in the range of composition given inparentheses; and that contains the following elements in the specifiedrange of composition given in parentheses: chromium (15 to 20 atomic %),molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to16 atomic %), carbon (3 to 16 atomic %), and the balance iron.

In another example, the source 302 of the deposition spray 304 can asource of amorphous metal that contains amorphous metal that comprises acomposite material made of amorphous metal that contains manganese (1.5to 2.9 atomic %), yttrium (0.1 to 7 atomic %), and silicon (0.3 to 3.1atomic %) in the range of composition given in parentheses; and thatcontains the following elements in the specified range of compositiongiven in parentheses: chromium (14.6 to 19.2 atomic %), molybdenum (2.3to 14 atomic %), tungsten (1.4 to 3 atomic %), boron (5.9 to 16 atomic%), carbon (3.7 to 15 atomic %), and (iron 41-76 atomic %).

New elemental compositions are being developed and tested for corrosionand wear resistant amorphous metals, along with composites thatincorporate these and other similar amorphous metals, and layered andgraded coatings with amorphous metals and ceramics. These and otheramorphous metal coatings can be produced as graded coatings, where thecoating gradually transitions from the metallic substrate material thatis being protected by the coating, to a pure amorphous metal coating, orto a amorphous metal multilayer coating, and eventually to an outerlayer, which provides extreme corrosion and wear resistance. The gradingcan be accomplished by gradually shifting from one amorphous metalpowder to another amorphous powder during the deposition operations.

Applicants are developing and testing the advanced formulations ofFe-based corrosion-resistant amorphous-metals that comprise a compositematerial made of amorphous metal that contains the following elements inthe specified range of composition given in parentheses: manganese (1.5to 2.9 atomic %), yttrium (0.1 to 7 atomic %), and silicon (0.3 to 3.1atomic %) in the range of composition given in parentheses; and thatcontains the following elements in the specified range of compositiongiven in parentheses: chromium (14.6 to 19.2 atomic %), molybdenum (2.3to 14 atomic %), tungsten (1.4 to 3 atomic %), boron (5.9 to 16 atomic%), carbon (3.7 to 15 atomic %), and (iron 41-76 atomic %).

These materials have lower critical cooling rates, and are thereforemore easily deposited in a glassy state, and have optimized elementalcompositions that exhibit much more stable passive film stability. Toavoid the experimental difficulties encountered with the earlythermal-spray coatings, these new materials were made into fully dense,pore-free samples with melt spinning. These new formulations, in theform of melt-spun ribbons and ingots, were tested in a salt fog chamberfor 24 cycles. Melt-spun ribbons of Alloy C-22 and Type 316L stainlesssteel were used as reference samples. In stark contrast to the earlythermal spray coatings of SAM40 (DAR40) and SAM40×3, none of these new“LDAR-series” ribbon samples exhibited any signs of corrosive attack.

These advanced formulations can be produced as either bulk alloys orcoatings. For example, melt spinning and arc melting with drop castingcan be used to render these materials as fully dense pore-free bulkalloys. Coatings can be produced with advanced thermal spray processes,or by physical vapor deposition processes such as magnetron sputteringor electron-beam evaporation. The materials can also be rendered as bulkalloys by using HVOF to form large plates on a flat mandrel. Neartheoretical density is achieved through precise control of powder sizewith atomization and classification.

X-Ray Diffraction of Drop-Cast Ingots

In addition to the melt-spinning process, arc-melted drop-cast ingots ofa wide variety of Fe-based amorphous metals were synthesized forcorrosion testing by ORNL. These ingots were cast into cylindricalmolds, thus forming long rods with a nominal diameter of 2-3millimeters. It has been learned that additions of 2-3 atomic percentyttrium or zirconium can enhance the glass-forming ability (GFA), andsubstantially lower the required critical cooling rate (CCR). Suchformulations are relatively easily cast as large-diameter (severalmillimeters) rods. The X-ray diffraction (XRD) pattern for drop-castingot of SAM1651, one version of this material, shows virtually nocrystalline structure. This is illustrated in FIG. 4. FIG. 4 shows anX-ray diffraction pattern for drop-cast ingot of SAM1651 (LDAR7 ORCBCTL1651), shows virtually no crystalline structure. Peak broadening ofall three HVOF coatings suggest presence of some fine crystallinephase(s) in the amorphous matrix. Peak broadening of all three HVOFcoatings suggest presence of some fine crystalline phases in theamorphous matrix.

X-ray diffraction (XRD) was used to show that the matrices of melt-spunribbons of SAM40 (DAR40) and drop-cast ingots of SAM1651 remainamorphous to 500° C., as shown in FIGS. 5A and 5B. However, XRD is noteffective for detecting dispersed crystalline phase(s) that account forless than 2 volume % of the material. The X-ray diffraction (XRD) ofFIGS. 5A and 5B shows that the matrices of melt-spun ribbons of SAM40(DAR40) parent material and drop-cast ingots of SAM1651 (LDAR7 ORCBCTL1651) remain amorphous to 500° C. However, XRD is not effective fordetecting dispersed crystalline phase(s) that account for less than 2volume % of the material. Electron microscopy was used to compensate forthis shortcoming.

Pore-Free Amorphous Coatings by Careful Control of Powder Size

Early high-velocity oxy-fuel (HVOF) coatings were found to have too muchporosity and residual crystalline structure for targeted DOD and DOEapplications. Therefore, a systematic study was undertaken to modify andoptimize the HVOF process so that fully dense, pore-free coatings couldbe produced. This optimization was successful.

A parametric study of the HVOF process was conducted with SAM40 (DAR40),with the mean particle size of the sprayed powder and the substratetemperature systematically varied, and is illustrated in FIG. 6. Whilecoatings produced with relatively large particles (≦54 μm) showedun-melted and un-consolidated particles embedded in the coating, withsubstantial porosity and poor interfacial bonding, coatings producedwith smaller particles (20 to 23 μm) are essentially homogeneous,pore-free and well-bonded. FIG. 6 shows a parametric study of the HVOFprocess conducted with SAM40 (DAR40), with the mean particle size of thesprayed powder and the substrate temperature systematically varied.While coatings produced with relatively large particles (>54 μm) showedun-melted and un-consolidated particles embedded in the coating, withsubstantial porosity and poor interfacial bonding, coatings producedwith smaller particles (20 to 23 μm) are essentially homogeneous,pore-free and well-bonded.

X-ray diffraction (XRD) data for the SAM40 (DAR40) coatings depositedwith HVOF during the parametric study represented by FIG. 6 are shown inFIGS. 7A, 7B, & 7C. From this data, it is evident that the coatingsproduced with smaller particles (25 μm) are more amorphous in nature,with fewer residual crystalline phases, than the coatings produced withlarger particles (38 to 53 μm). FIGS. 7A, 7B, & 7C show X-raydiffraction SAM40 (DAR40) deposited with HVOF during the parametricstudy show that the coatings produced with smaller particles (25 μm) aremore glassy, with fewer residual crystalline phases, than the coatingsproduced with larger particles (38 to 53 μm).

Initial Images of Aged Melt-Spun Ribbons and Drop-Cast Ingots

Elemental mapping of melt-spun ribbons shows the formation ofcrystalline phases in after a 1-hour exposure at 800° C. Substantialcrystallization occurs after a 1-hour exposure at 1000° C. in FIG. 8.FIG. 8 shows Elemental mapping shows the formation of crystalline phasesin melt-spun ribbons of SAM40 (DAR40) after a 1-hour exposure at 800° C.Substantial crystallization occurs after a 1-hour exposure at 1000° C.In contrast, elemental mapping drop cast ingots of SAM1651 shows noformation of crystalline phases in arc-melted drop-cast ingots ofSAM1651 after a 1-hour exposure at 800° C., but the onset ofcrystallization after a 1-hour exposure at 1000° C. Small yttrium oxideparticles remained unaffected in the matrix as illustrated in FIG. 9.FIG. 9 shows elemental mapping shows no formation of crystalline phasesin arc-melted drop-cast ingots of SAM1651 after a 1-hour exposure at800° C., but the onset of crystallization after a 1-hour exposure at1000° C. Small yttrium oxide particles remained unaffected in thematrix. Progress made is illustrated with FIG. 10. FIG. 10 shows acomparison of the original SAM40 (DAR40) formulation in 2004 to theSAM1651 (LDAR7 OR CBCTL1651) formulation in 2005, in regard to thermalstability at 800° C. and coating morphology.

Thermal Analysis

A summary of the thermal analysis data for melt-spun ribbons is given inTable 2 below, which shows all of the acquired information to date onFe-alloys investigated during the first year of this project. The tablelists glass transition temperature T_(g) crystallization temperatureT_(x) (of the amorphous phase), onset of melting T_(m) and liquidustemperature T_(l). In addition, a rough measure of the glass formingability is listed as Tr_(g), the reduced glass transition temperaturedefined as T_(g)/T_(l) where temperatures are given in degrees Kelvin.Good glass forming alloys have high reduced glass transitiontemperatures of about 0.55-0.60. There are other ways of defining theglass-forming ability (GFA) based on a thermal analysis; however, theyall have in common that one method may fit a particular alloy betterthan a different method. Caution is therefore advised when using thermalanalysis as means of estimating GFA.

TABLE 2 Alloy T_(g) (° C.) T_(x) (° C.) T_(m) (° C.) T_(L) (° C.) T_(rg)(° C.) SAM35 545-565 613 1074 1350 0.51 SAM40 568-574 623 1110 1338 0.53SAM40X3 561-567 630 1130 1260 0.55 SAM1X1 not clear 612 1121 min. 1270N.A. SAM1X3 560 589 1119 min. 1300 0.53 SAM1X5 540 572 1115 min. 13000.52 SAM1X7 510 545 1112 min. 1300 0.50 SAM2X1 575 620 1124 1190-12100.57 SAM2X3 578 626 1131 1190-1210 0.57 SAM2X5 579 628 1133 1190-12100.57 SAM2X7 573 630 1137 1190-1210 0.57 SAM3X1 560 614 1108 min. 13200.52 SAM3X3 573 659 1138 min. 1380 0.51 SAM3X5 590 677 1143 min. 14000.52 SAM3X7 not clear 697 1164 min. 1420 SAM4X1 573 621 1135 min. 13000.54 SAM4X3 568 623 1146 min. 1320 0.53 SAM4X5 580 623 1194 1290 0.55SAM4X7 558 616 1198 1255 0.54 SAM5X1 570 622 1134 min. 1360 0.52 SAM5X3575 641 1147 min. 1410 0.50 SAM5X5 596 659 1193 min. 1420 0.51 SAM6 580623²⁾ 995 1238-1250 0.56 SAM7 584 653²⁾ 1121 1290 0.55 SAM8 565 637²⁾1137 1350-1370 0.52 SAM9 572 677²⁾ 1146 1223 0.56 SAM10 535 568¹⁾ 12101350-1370 0.50 SAM11 535 572¹⁾ 1202 1365-1395 0.49

Note that a comparison of h for different wedge-casts can be usedqualitative to describe heat transfer properties of the sample alloy,since it is expected that the overall h should not be very different formodest changes in the composition. Heat transfer at the melt-moldinterface dictates the overall cooling behavior through an apparenttemperature dependent heat transfer coefficient.

Predicted Pourbaix Diagrams

The predicted Pourbaix diagrams for SAM1651 and LDAR8 (SAM1651 withtungsten) in synthetic seawater at near-ambient temperature (30° C.) areshown in FIGS. 11A and 11B. FIGS. 11A and 11B show predicted Pourbaixdiagrams for

SAM1651 and SAM1651+W amorphous metal formulations in synthetic seawaterat near-ambient temperature (30° C.). In the later case, the presence oftungsten leads to the formation of FeWO₄ and WO₂(OH)₂, while thepresence of molybdenum leads to the formation of MoO₂ and MO₃. Chromiumand iron oxides (Cr₂O₃ and Fe₂O₃) also contribute to passive filmstability. Under alkaline conditions, stable Y₂O₃ and NaO4W surfacephases are predicted. Such predicted Pourbaix diagrams, and thecapability developed to make such predictions, is clear evidence thatMilestone 1 has been met.

In the later case, the presence of tungsten leads to the formation ofFeWO₄ and WO₂(OH)₂, while the presence of molybdenum leads to theformation of MoO₂ and MO₃. Chromium and iron oxides (Cr₂O₃ and Fe₂O₃)also contribute to passive film stability. Under alkaline conditions,stable Y₂O₃ and NaO₄W surface phases are predicted. Such predictedPourbaix diagrams, and the capability developed to make suchpredictions, is clear and concrete evidence that Milestone 1 has beenmet.

The predicted Pourbaix diagrams for SAM1651 (LDAR7 OR CBCTL1651) inconcentrated calcium chloride brines at 30 and 90° C. are shown in FIGS.12A and 12B. FIGS. 12A and 12B show predicted Pourbaix diagrams forSAM1651 (LDAR7 OR CBCTL1651) amorphous metal formulations inconcentrated calcium chloride brines at 30 and 90° C. Underacidic-to-neutral conditions, MoO₂, MO₃, CaO-MO₃, Cr₂O₃ and Fe₂O₃contribute to passive film stability. Under alkaline conditions, stableY₂O₃ and Ca(OH)₂ surface phases are also predicted.

Under acidic-to-neutral conditions, MoO₂, MO₃, CaO-MO₃, Cr₂O₃ and Fe₂O₃contribute to passive film stability. Under alkaline conditions, stableY₂O₃ and Ca(OH)₂ surface phases are also predicted.

The predicted Pourbaix diagrams for LDAR8, with tungsten at aconcentration of 3 atomic percent, in concentrated calcium chloridebrines at 105 and 118° C. are shown in FIGS. 13A and 13B. FIGS. 13A and13B show predicted Pourbaix diagrams for +W amorphous metal formulationsin concentrated calcium chloride brines at 105 and 118° C. The presenceof tungsten leads to the formation of FeWO₄ and WO₂(OH)₂, while thepresence of molybdenum leads to the formation of MoO₂, MO₃ and CaO-MO₃.Chromium and iron oxides (Cr₂O₃ and Fe₂O₃) also contribute to passivefilm stability. Under alkaline conditions, stable Y₂O₃ and Ca(OH)₂surface phases are predicted.

The presence of tungsten leads to the formation of FeWO₄ and WO₂(OH)₂,while the presence of molybdenum leads to the formation of MoO₂, MO₃ andCaO-MO₃. Chromium and iron oxides (Cr₂O₃ and Fe₂O₃) also contribute topassive film stability. Under alkaline conditions, stable Y₂O₃ andCa(OH)₂ surface phases are predicted.

Electrochemical Corrosion Testing

Cyclic polarization (CP) is used as a means of measuring the criticalpotential (E_(critical)) of corrosion resistant materials, relative totheir open-circuit corrosion potential (E_(corr)). Spontaneous breakdownof the passive film and localized corrosion require that theopen-circuit corrosion potential exceed the critical potential.

In the published scientific literature, different bases exist fordetermining the critical potential from electrochemical measurements.Some have defined the critical potential for crevice corrosion of Alloy22 as the point where the current density increases to 1 to 10 mA/cm²(10⁻⁶ to 10⁻⁵ A/cm²) during the forward (anodic) scan, whereas othersdefine the repassivation potential as the point where the currentdensity drops to 0.1 to 1 mA/cm² (10⁻⁶ to 10⁻⁷ A/cm²), and use therepassivation potential as a conservative estimate of the criticalvalue.

Cyclic polarization measurements have been based on a procedure similarto ASTM G-5, with slight modification [American Society for Testing andMaterials]. For example, ASTM G-5 calls for an electrolyte of 1N H₂SO₄,whereas natural seawater, synthetic bicarbonate brines, syntheticsulfate-chloride brines, 4M NaCl solutions, and 5M CaCl₂ solutions withvarious levels of nitrate were used in this study. The compositions ofthe synthetic brines are given in the literature. Furthermore, ASTM G-5calls for the use of de-aerated solutions, whereas aerated andde-aerated solutions were used here. After a 24-hour hold period, duringwhich the open circuit corrosion potential is determined, the potentialis scanned in the positive (anodic) direction from a level slightly morenegative than the corrosion potential (cathodic limit), to a reversalpotential (E_(rev)) near that required for oxygen evolution (anodiclevel). During the positive scan, anodic oxidation peaks may be observed(centered at E_(peak)) that have been correlated with the oxidation ofmolybdenum at the alloy surface (passive film), as well as currentexcursions that are usually associated with breakdown of the passivefilm. During the negative (cathodic) scan, a hysteresis loop will beobserved in cases where passivity has been lost. As the scan continues,the current density may eventually decrease to a level equivalent tothat experienced during the positive scan, and indicative of reformationof the passive film. The potential at which this occurs is known as therepassivation potential (E_(rp)).

A temperature-controlled, borosilicate glass (Pyrex), electrochemicalcell was used. This cell had three electrodes, a working electrode (testspecimen), the reference electrode, and the counter electrode. Astandard silver silver-chloride electrode, filled with near-saturationpotassium chloride solution, was used as the reference, and communicatedwith the test solution via a Luggin probe placed in close proximity tothe working electrode, thereby minimizing Ohmic losses. Numericalcorrections for the reference electrode junction potential have beenestimated, and have been found to be insignificant. The electrochemicalcell was equipped with a water-cooled junction to maintain referenceelectrode at ambient temperature, thereby maintaining integrity of thepotential measurement, and a water-cooled condenser to prevent the lossof volatile species from the electrolyte.

The resistance to localized corrosion is quantified through measurementof the open-circuit corrosion potential (E_(corr)), the breakdownpotential (E_(crit)) and the repassivation potential (E_(rp)). Thegreater the difference between the open-circuit corrosion potential andthe repassivation potential (ΔE), the more resistant a material is tomodes of localized corrosion such as pitting and crevice corrosion.

Competing methodologies exist for the interpretation of experimentaldata in terms of the critical potential (E_(crit)). Method A strives toidentify the potential where the passive film disappears during theforward (anodic) potential scan. The loss of passivity is indicated by asudden, dramatic increase in the measured current density. The currentdensity corresponding to a complete loss of passivity is assumed to beapproximately 20 or 200 mA/cm². The breakdown potential may be the bestestimate of the true critical potential, since it corresponds to theonset of passive film destabilization. Methods B and C strive toidentify the potential where the passive film reappears during thenegative (cathodic) potential scan. Repassivation is indicated by asudden, precipitous decrease in the measured current density, to levelsindicative of an intact passive film. Method C relies on no arbitrarythreshold, and is therefore preferred.

Method A—Initial Breakdown of Passive Film

-   -   Critical Potential (E_(crit))=Breakdown Potential (E20 or E200)    -   Based Threshold Current Density of 20 or 200 mA/cm²

Method B—Repassivation of Surface

-   -   Critical Potential (E_(crit))=Repassivation Potential (ER1 or        ER²)    -   Based Threshold Current Density of 1 or 2 mA/cm²

Method C—Repassivation of Surface

-   -   Critical Potential (E_(crit))=Repassivation Potential (ERP)    -   Intersection of Forward Scan with Hysteresis Loop (Cross-Over

Point)

FIG. 14 shows an actual cyclic polarization curve for Alloy C-22 in 5MCaCl₂ at 105° C., with three methodologies illustrated for determiningthe threshold potential for the initiation of localized corrosion inperformance assessment models. Method A is based upon the criticalpotential at which the passive film breaks down (current excursion, 2 or20 mA/cm²). FIG. 14 is an actual cyclic polarization curve for AlloyC-22 in 5M CaCl₁₂ at 105° C., showing three methodologies fordetermining the threshold potential for the initiation of localizedcorrosion in performance assessment models. Method A is based upon thecritical potential at which the passive film breaks down (currentexcursion, 2 or 20 mA/cm²). Method B is based upon the repassivationpotential, which in turn is based upon an arbitrary threshold (1 or 2mA/cm²). Method C is based upon the repassivation potential, determinedfrom the intersection of the hysteresis loop with the forward scan.

Method B is based upon the repassivation potential, which in turn isbased upon an arbitrary threshold (1 or 2 mA/cm²). Method C is basedupon the repassivation potential, determined from the intersection ofthe hysteresis loop with the forward scan, and is preferred.

A premise of this research is that the corrosion-resistance of Fe-basedamorphous metals can be improved by systematic addition of alloyingelements such as chromium, molybdenum, and tungsten, all of which areknown to enhance passive film stability (FIG. 15). FIG. 15 shows thepredicted role of chromium, molybdenum, tungsten and titanium on passivefilm stability, based upon knowledge of the Pourbaix diagrams of each ofthese alloying elements. This Figure was based on an earlier Figureprepared for presentation to the Nuclear Waste Technical Review Board,but without any specific reference to HVOF SAM. This was an earlierprediction (cartoon depiction of the yet-to-be-measured performance ofSAM2×5 (LDAR2×5) and SAM1651 (LDAR7 OR CBCTL1651)). Such elementaladditions account for the observed difference in the corrosionresistance of Type 316L stainless steel, and nickel-based Alloy C-22(FIGS. 16A and 16B). FIGS. 16A and 16B show early data of Farmer et alclearly show the benefits of Mo additions on the enhancement of AlloyC-22 corrosion resistance in comparison to that of Type 316L stainlesssteel. This recognized beneficial effect of molybdenum has been fullyexploited in the enhancement and optimization of the early DAR-typecompositions of NanoSteel, thereby rendering them far more corrosionresistant than first observed.

Cyclic Polarization of Published SAM1651 (LDAR7 OR CBCTL1651)Composition (Joe Poon Alloy) in Hot CaCl2 Brines

Cyclic polarization testing of reference materials such as Alloy C-22and various Fe-based amorphous metals were conducted in 5M CaCl2 at 105°C. Data for wrought nickel-based Alloy C-22 (N06022) and iron-basedSAM1651 (LDAR7 OR CBCTL1651) amorphous metal ingot are compared in FIG.17. FIG. 17 shows Cyclic polarization of wrought nickel based Alloy C-22(N06022) and iron-based amorphous metal SAM1651 (LDAR7 OR CBCTL1651)ingot in 5M CaCl₂ at 105° C. Alloy C-22 shows catastrophic breakdown ofthe passive film at 100 mV vs. Ag/AgCl, which causes a very largehysteresis loop. During the reverse scan, repassivation occurs at arelatively low potential (−150 to −200 mV). While there was catastrophicbreakdown of the Alloy C-22 at very low potential (100 to 200 mV vs.Ag/AgCl), no breakdown of the passive film on ingot was observed, evenat potentials approaching that required for oxygen evolution.

The data for Alloy C-22 show a breakdown of the passive film at 100 mV,which causes a very large hysteresis loop. During the reverse scan,repassivation occurs at a relatively low potential (−150 to −200 mV vs.Ag/AgCl). These data indicate that Alloy C-22 has relatively poorresistance to localized corrosion in the test environment. In sharpcontrast to Alloy C-22, the SAM1651 (LDAR7 OR CBCTL1651) ingot showed nobreakdown of the passive film, even at potentials approaching thatrequired for oxygen evolution. It is therefore concluded that thecorrosion resistance of the amorphous metal is superior to that of AlloyC-22 in hot concentrated calcium chloride solution.

Cyclic polarization data for a wide range of alloy compositions in hotcalcium chloride are summarized in FIG. 18. FIG. 18 shows various alloysamples, ranked based upon their measured resistance to localizedcorrosion (ΔE=E_(corr)−E_(rp)) in 5M CaCl2 at 105° C. With the exceptionof the P-containing Fe-based amorphous metal (Pang et al.), most of theamorphous metals performed very well in this aggressive environment. Incontrast, the performance of the wrought nickel-based Alloy C-22(N06022) was relatively poorly. The LDAR8 (SAM8) formulation usesSAM1651 (LDAR7 OR CBCTL1651); Y-containing, high-Mo Fe-based amorphousmetal) as the parent material, with the addition of tungsten at 3 atomicpercent. The repassivation potential for SAM8 in this aggressiveenvironment (300-400 mV vs. Ag/AgCl) is substantially higher than thatfor Alloy C-22 (−100 mV vs. Ag/AgCl). The LDAR6 (SAM6) formulation hasthe same nominal elemental composition as the P-containing Fe-basedamorphous metal formulation discussed in the literature by Pang et al.The repassivation potential for LDAR6 (SAM6) in this aggressiveenvironment (400 mV vs. Ag/AgCl) is substantially higher than that forAlloy C-22 (−100 mV vs. Ag/AgCl).

Cyclic Polarization of Published SAM1651 (LDAR7 OR CBCTL1651)Composition (Joe Poon Alloy) in Seawater Environments

Cyclic polarization testing of reference materials and Fe-basedamorphous metals were conducted in Half Moon Bay seawater at varioustemperatures, ranging from 30 to 90° C., as well as in Key West seawaterat ambient temperature. A comparison of the cyclic polarization curvesfor a SAM1651 (LDAR7 OR CBCTL1651) amorphous metal ingot, a sample ofwrought nickel-based Alloy C-22, and a sample of thermal spray (HVOF)C-22 in ambient temperature Half Moon Bay seawater is shown in FIG. 19.FIG. 19 shows a comparison of the cyclic polarization curves for SAM1651(LDAR7 OR CBCTL1651) amorphous metal ingot, a sample of wroughtnickel-based Alloy C-22, and a sample of thermally spray Alloy C-22 inambient temperature, Half Moon bay seawater is shown. The SAM1651 (LDAR7OR CBCTL1651) amorphous metal had better corrosion resistance than bothwrought and HVOF alloy C-22.

The curves for the SAM1651 (LDAR7 OR CBCTL1651) ingot and wrought AlloyC-22 have very small hysteresis loops, and repassivation potentialsclose to the potential required for oxygen evolution. It is thereforeconcluded that Y-containing Fe-based SAM1651 (LDAR7 OR CBCTL1651)amorphous metal performs very well in ambient temperature seawater, withperformance comparable to wrought Alloy C-22. The data in thisFigure-PVP also show that the corrosion resistance of Alloy C-22 issubstantially degraded during the thermal spray process.

FIG. 20 shows a ranking of various alloy samples, based upon theirmeasured resistance to localized corrosion (ΔE=E_(corr)−E_(rp)) in HalfMoon Bay seawater at 90° C. FIG. 20 shows various alloy samples, rankedbased upon their measured resistance to localized corrosion(ΔE=E_(corr)−E_(rp)) in Half Moon Bay seawater at 90° C. Most of theamorphous-samples performed very well, with the arc-melted drop-castingot of SAM1651 (LDAR7 OR CBCTL1651) showing the best performance. Theelectrochemical performance of these materials in seawater was as goodas Alloy C-22, and superior to Type 316L stainless steel. Referencesamples of Type 316L stainless steel do not perform as well in thisenvironment as ingots and melt-spun ribbons of Fe-based amorphousmetals. Most of the amorphous-samples performed very well, with thearc-melted drop-cast ingot of LDAR7 SAM1651 (LDAR7 OR CBCTL1651) andother Y-containing variants of the parent material (LDAR3×3 or SAM3×3)showing the best performance. The Mo-containing variants also showedoutstanding performance. The previously published P-containing materialperformed well, but not as well as the Y- and Mo-containing variants ofSAM40 (DAR40).

Electrochemical Corrosion Testing of Metallic Glasses with CriticalLevels of Yttrium and Tungsten

Ingots and melt-spun ribbons of the Y- and Mo-containing Fe-basedamorphous metals have no grain boundaries, and therefore have morecorrosion resistance in than the more expensive nickel-based Alloy C-22.While the passive film on nickel-based C-22 undergoes breakdown in 5MCaCl₂ at 105° C. at low potential, the passive film on the new Fe-basedamorphous metal remains stable at a potential above that required foroxygen evolution. Electrochemical tests have proven that corrosionperformance superior to wrought and thermally sprayed coatings ofnickel-based Alloy C-22 can be achieved with the new iron-basedamorphous metals. For example, the passive film on wrought Alloy C-22undergoes breakdown at 100 to 200 mV vs. Ag/AgCl in 5M CaCl₂ at 105° C.,whereas SAM1651 (LDAR7 OR CBCTL1651) maintains stable passivity, even asthe potential is increased to levels approaching that required foroxygen evolution. These materials are far superior to thermal-spraycoatings of Alloy C-22 in seawater. While it has not been possible torender Alloy C-22 as a corrosion resistant, thermal spray coating, suchpossibilities do exist with the amorphous metal formulations. Thecurrent Fe-based amorphous metals include specific elements known toimpart corrosion and oxidation resistance, such as Cr, Mo, W. Additionsof Y and Zr improve glass formability, while forming protective oxidescales at high temperature. In the future, the addition of titanium mayalso lead to improved passive film stability at higher temperatures, andis being explored.

This cyclic polarization curve for a melt-spun ribbon of LDAR8 in 5MCaCl2 at 105° C. is shown in FIG. 21. FIG. 21 shows cyclic polarizationcurve is for a melt-spun ribbon of LDAR8 in 5M CaCl2 at 105° C. TheLDAR8 formulation uses SAM1651 (LDAR7 OR CBCTL1651) (Y-containing,high-Mo Fe-based amorphous metal) as the parent material, with theaddition of tungsten at 3 atomic percent. The repassivation potentialfor LDAR8 in this aggressive environment (300-400 mV vs. Ag/AgCl) issubstantially higher than that for Alloy C-22 (−100 mV vs. Ag/AgCl). TheLDAR8 formulation uses SAM1651 (LDAR7 OR CBCTL1651) (Y-containing,high-Mo Fe-based amorphous metal) as the parent material, with theaddition of tungsten at 3 atomic percent. The repassivation potentialfor LDAR8 in this aggressive environment (300-400 mV vs. Ag/AgCl) issubstantially higher than that for Alloy C-22 (−100 mV vs. Ag/AgCl).

Cyclic polarization testing of reference materials and Fe-basedamorphous metals were conducted in hot, concentrated, calcium chloridesolution. Unless otherwise stated, conducted in 5M CaCl2 at 105° C. Acompilation of the measured values of the open circuit corrosionpotential (E_(corr)), the potential coinciding with the anodic oxidationpeak (E_(peak)), the repassivation potential (E_(rp)), and thepenetration rate based upon the maximum passive current density (dx/dt)is given in Table 3.

TABLE 3 Various Alloys at 105 Degrees Centigrade - No Nitrate E_(corr)E_(rp) mV mV E_(rp) − E_(corr) dx/dt Material (Ag/AgCl) (Ag/AgCl) mVcm/yr LDAR1X7 −396 −321 75 7.31E−04 LDAR6 (Inoue) 125 407 282 2.31E−03Alloy C-22 −482 −110 372 1.06E−02 LDAR2X3 −327 363 690 2.31E−03 LDAR8−327 363 690 2.91E−03 LDAR2X7 −109 671 780 7.31E−03 LDAR2X5 −301 546 8471.84E−03 LDAR2X7 −178 677 855 4.61E−03 LDAR2X3 −151 713 864 4.61E−03LDAR7 (CBCTL1651) −164 705 869 2.91E−01 LDAR10 (LMDAR4022) −300 610 9107.31E−03 LDAR11 (LMDAR1922) −323 622 945 2.31E−03 LDAR3X1 −281 666 9474.61E−03 LDAR5X1 −352 601 953 9.21E−04 LDAR2X5 −408 548 956 1.84E−04LDAR1X3 −409 579 988 1.46E−03 LDAR3X3 −339 692 1031 2.31E−03

Cyclic polarization testing of reference materials and Fe-basedamorphous metals were conducted in Half Moon Bay seawater at varioustemperatures, ranging from 30 to 90° C., as well as in Key West seawaterat ambient temperature. A compilation of the measured values of the opencircuit corrosion potential (E_(corr)), the potential coinciding withthe anodic oxidation peak (E_(peak)) the repassivation potential(E_(rp)), and the penetration rate based upon the maximum passivecurrent density (dx/dt) is given in Table 4,

TABLE 4 E_(corr) E_(rp) E_(rp) − E_(corr) dx/dt Material ProcessComposition (Ag/AgCl) (Ag/AgCl) mV cm/yr Seawater at 30 DegreesCentigrade DAR40 HDIF Fe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −668−645 23 CBAM83 Arc-Melt Drop-Cast Ingot Fe-Based −165 −92 73 4.61E−03DAR40 MSR Fe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −275 −126 1491.84E−01 316L Wrought Fe—Cr—Mo −227 −227 190 3.67E−03 C22 HVOF Fe—Cr—Mo−392 −127 265 1.84E−01 LDAR2X5 MSR (DAR40)₉₅ + Mo₅ −19 894 913 9.21E−04DAR40 HVOF Fe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −94 830 9249.21E−02 DAR35 HVOF Fe_(54.5)Mn₂Cr₁₅Mo₂W_(1.5)B₁₆C₄Si₅ −248 720 9681.16E−02 LDAR6 MSR Fe₄₃Cr₁₆Mo₁₆B₅C₁₀P₁₀ −160 884 1044 4.61E−04 (Inoue)LDAR10 MSR Fe_(57.3)Cr_(21.4)Mo_(2.6)W_(1.8)B_(16.9) −233 858 10912.31E−03 (LMDAR4022) LDAR1X7 MSR (DAR40)₉₃ + Ni₇ −353 815 1168 1.84E−03LDAR5X1 MSR (DAR40)₉₉ + Zr₁ −275 930 1205 1.84E−03 DAR40X3 HVOFFe_(50.7)Mn_(1.9)Cr_(18.4)Mo_(5.4)W_(1.6)B_(15.5)C_(3.9)Si_(2.4) −370878 1248 4.61E−01 CBCTL1651 Arc-Melt Drop-Cast Ingot Fe₄₈Mo₁₄Cr₁₅Y₂C₁₅B₆−376 881 1257 4.61E−02 LDAR1X3 MSR (DAR40)₉₇ + Ni₃ −310 972 12821.16E−03 LDAR7 MSR Fe₄₈Mo₁₄Cr₁₅Y₂C₁₅B₆ −384 908 1292 9.21E−04(CBCTL1651) Seawater at 60 Degrees Centigrade 316L Wrought Fe—Cr—Mo −241−241 122 7.31E−03 C22 HVOF Fe—Cr—Mo −415 −222 193 7.31E−01 DAR40 HVOFFe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −362 750 1112 2.31E−01DAR35 HVOF Fe_(54.5)Mn₂Cr₁₅Mo₂W_(1.5)B₁₆C₄Si₅ −360 752 1112 7.31E−02DAR40 MSR Fe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −274 822 10961.84E−03 Seawater at 90 Degrees Centigrade DAR35 HVOFFe_(54.5)Mn₂Cr₁₅Mo₂W_(1.5)B₁₆C₄Si₅ −505 −409 96 316L Wrought Fe—Cr—Mo−210 none 130 1.84E−02 DAR40 HVOFFe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −504 −346 158 7.31E−02FBAM117 Arc-Melt Drop-Cast Ingot Fe-Based 336 591 255 9.21E−03 C22 HVOFFe—Cr—Mo −576 −277 299 1.46E+00 LDAR6 MSR Fe₄₃Cr₁₆Mo₁₆B₅C₁₀P₁₀ −97 560657 2.31E−03 (Inoue) DAR40 MSRFe_(52.3)Mn₂Cr₁₉Mo_(2.5)W_(1.7)B₁₆C₄Si_(2.5) −115 716 831 2.91E−03 LDAR7MSR Fe₄₈Mo₁₄Cr₁₅Y₂C₁₅B₆ −313 543 856 3.67E−03 (CBCTL1651) LDAR2X7 MSR(DAR40)₉₃ + Mo₇ −182 680 862 1.84E−03 LDAR8 MSR (CBCTL1651)97 + W3 −355553 908 4.61E−03 LDAR2X3 MSR (DAR40)₉₇ + Mo₃ −241 693 934 2.91E−03LDAR4X7 MSR (DAR40)₉₃ + Ti₇ −21 1000 1021 4.61E−03 LDAR5X1 MSR(DAR40)₉₉ + Zr₁ −198 823 1021 3.67E−03 LDAR2X7 MSR (DAR40)₉₃ + Mo₇ −234805 1039 3.67E−03 LDAR11 MSR DAR40 Variant −287 771 1058 3.67E−03(LMDAR1922) LDAR10 MSR Fe_(57.3)Cr_(21.4)Mo_(2.6)W_(1.8)B_(16.9) −296807 1103 5.81E−03 (LMDAR4022) LDAR4X5 MSR (DAR40)₉₅ + Ti₅ −224 910 11343.67E−03 LDAR2X5 MSR (DAR40)₉₅ + Mo₅ −203 949 1152 2.31E−03 LDAR3X3 MSR(DAR40)₉₇ + Y₃ −371 789 1160 1.84E−03 CBCTL1651 Arc-Melt Drop-Cast IngotFe₄₈Mo₁₄Cr₁₅Y₂C₁₅B₆ −270 944 1214 2.31E−01 Salt Fog Testing of PublishedSAM1651 (LDAR7 OR CBCTL1651) Composition (Also known as the Joe PoonAlloy)

The salt fog test was used to compare various wrought ant thermal-sprayalloys, melt-spun ribbons, arc-melted drop-cast ingots, andthermal-spray coatings for their susceptibility to corrosion by saltsprays, like those that might be encountered aboard naval ships (thistest is also known as the “salt spray” test). The most recent tests havefocused on refined, state-of-the-art Fe-based amorphous-metalformulations, in the form of arc-melted drop-cast ingots, melt-spunribbons, and high-velocity oxy-fuel coatings with no significantporosity and near theoretical density. In contrast, the first testsfocused on early thermal-spray coatings, which had residual porosity andcrystalline structure, and lower resistance to corrosion.

Both salt fog tests were conducted according to ASTM B117 “Standard TestMethod of Salt Spray (Fog) Testing.” A General Motors (GM) test cycle,GM9540P, was used in both tests. The performance of the testdevelopmental amorphous metal samples was evaluated by qualitativecomparison to baseline or reference samples. Four types of referencesamples were included to establish baseline performance. Thesereferences include: Type 316L stainless steel, nickel-based Alloy C-22(N06022), Ti Grade 7, and the 50:50 nickel-chromium binary.

During the initial phase of the project, coatings of Type 316L stainlesssteel, nickel-based Alloy C-22, SAM40 (DAR40), SAM40×3 (SAM40×3) weredeposited on stainless steel substrates (Type 316L) with thehigh-velocity oxy-fuel (HVOF) process. During salt-fog testing, therewas no significant rusting of the reference samples. Substantial rustingof early HVOF coatings of SAM40 (DAR40) and Type 316L stainless steelwas observed after only 13 cycles. There may have also been some slightrust formation on the Alloy C-22 HVOF coating. The rusting of theseearly coatings is attributed to non-optimal elemental composition,residual porosity, and partial devitrification during the thermal-sprayprocess.

During the past year, several advanced formulations of Fe-basedcorrosion-resistant amorphous-metals have been produced. Some of thesematerials have lower critical cooling rates than the early SAM40 (DAR40)parent material, and may therefore be more easily deposited in a glassystate, and have optimized elemental compositions that exhibit much morestable passive film stability. As illustrated by FIGS. 22A, 22B and 22C,early thermal-spray coatings of Type 316L stainless steel and the SAM40(DAR40) parent material showed relatively severe corrosive attack afteronly 13 cycles in the ASTM B117 salt fog test. FIGS. 22A, 22B and 22Cshow early thermal-spray coatings of Type 316L stainless steel and theSAM40 (DAR40) parent material showed relatively severe corrosive attackafter only 13 cycles in the ASTM B117 salt fog test. However, several ofthe new Fe-based amorphous metal coatings, including SAM1651 (LDAR7 ORCBCTL1651) and SAM2×5 (LDAR2×5), have shown no corrosion, even aftermore than 30 cycles in this aggressive environment. It is thereforebelieved that these new materials will provide substantial benefit insome Naval applications. However, several of the new Fe-based amorphousmetal coatings, including LFST7, SAM1651 (LDAR7 OR CBCTL1651) and SAM2×5(LDAR2×5), have shown no corrosion, even after more than 30 cycles inthis aggressive environment. It is therefore believed that these newmaterials will provide substantial benefit in some Naval applications.FIGS. 22D, 22E, 22F, and 22G show early thermal-spray coatings of Type316L stainless steel and the SAM40 (DAR40) parent material showedrelatively severe corrosive attack after only 13 cycles in the ASTM B117salt fog test. However, several of the new Fe-based amorphous metalcoatings, including SAM1651 (LDAR7 OR CBCTL1651) and SAM2×5 (LDAR2×5),have shown no corrosion, even after more than 30 cycles in thisaggressive environment. It is therefore believed that these newmaterials will provide substantial benefit in some Naval applications.

Early HVOF coatings of DAR35, SAM40 (DAR40) and SAM40×3 (SAM35, SAM40(DAR40) and SAM40×3) had non-optimal elemental compositions, and wereproduced with non-optimal thermal spray parameters (powder size, gunpressure, and particle velocity), and exhibited light rusting after 13cycles in the classic salt fog test. However, additional work withoptimized elemental compositions of these Fe-based amorphous metals, andsamples in the form of fully dense pore-free materials, has shown nocorrosion after 24 cycles in this aggressive test. The most promisingformulations at the present time are believed to be SAM2×5 (LDAR2×5) andSAM1651 (LDAR7 OR CBCTL1651). Salt-fog testing of HVOF coatings of thesematerials showed no corrosion after more than 30 cycles in the salt fogtest. Such performance cannot be achieved with thermally sprayed Type316L stainless steel, as this material loses most of its desirablecorrosion-resistance during the thermal spray process. To a lesserextent, similar difficulties are encountered during the thermal sprayingof Alloy C-22.

While the invention may be susceptible to various modifications andalternative forms, specific embodiments have been shown by way ofexample in the drawings and have been described in detail herein.However, it should be understood that the invention is not intended tobe limited to the particular forms disclosed. Rather, the invention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the invention as defined by the followingappended claims.

1. A method of coating a surface, comprising the steps of: providing asource of amorphous metal that contains manganese (1 to 3 atomic %),yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in therange of composition given in parentheses; and that contains thefollowing elements in the specified range of composition given inparentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic%), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to16 atomic %), and the balance iron; and applying said amorphous metal tothe surface by a spray.
 2. The method of coating a surface of claim 1wherein said step of applying said amorphous metal to the surface by aspray produces the coating and the coating contains the followingelements in the specified range of composition given in parentheses:manganese (1.5 to 2.9 atomic %), yttrium (0.1 to 7 atomic %), silicon(0.3 to 3.1 atomic %), chromium (14.6 to 19.2 atomic %), molybdenum (2.3to 14 atomic %), tungsten (1.4 to 3 atomic %), boron (5.9 to 16 atomic%), carbon (3.7 to 15 atomic %), and (iron 41-76 atomic %).
 3. Themethod of coating a surface of claim 1 wherein said step of applyingsaid amorphous metal to the surface by a spray produces the coating,wherein said amorphous metal has a matrix of yttrium oxide, and whereinthe coating contains the following elements in the specified range ofcomposition given in parentheses: manganese (1.5 to 2.9 atomic %),yttrium (0.1 to 7 atomic %), silicon (0.3 to 3.1 atomic %), chromium(14.6 to 19.2 atomic %), molybdenum (2.3 to 14 atomic %), tungsten (1.4to 3 atomic %), boron (5.9 to 16 atomic %), carbon (3.7 to 15 atomic %),and (iron 41-76 atomic %).
 4. The method of coating a surface of claim 1wherein said step of applying said amorphous metal to the surface by aspray comprises using cold-spray to deposit said amorphous metal on thesurface.
 5. The method of coating a surface of claim 1 wherein said stepof applying said amorphous metal to the surface by a spray comprisesusing cold-spray and a soft corrosion-resistant binder to deposit saidamorphous metal on the surface.
 6. The method of coating a surface ofclaim 1 wherein said step of applying said amorphous metal to thesurface by a spray comprises applying said amorphous metal to thesurface by deposition.
 7. The method of coating a surface of claim 1wherein said step of applying said amorphous metal to the surface by aspray comprises applying said amorphous metal to the surface byelectrochemical deposition.
 8. The method of coating a surface of claim1 wherein said step of applying said amorphous metal to the surface by aspray comprises applying said amorphous metal to the surface by sputterdeposition.
 9. The method of coating a surface of claim 1 wherein saidstep of applying said amorphous metal to the surface by a spraycomprises applying said amorphous metal to the surface by thermal spraydeposition.
 10. The method of coating a surface of claim 1 wherein saidstep of applying said amorphous metal to the surface by a spraycomprises electrochemical deposition, sputter deposition, evaporation,melt spinning, arc melting and drop casting, gas atomization, cryogenicco-milling of elements, thermal spray deposition, cold spray deposition,or induction-heated cold-spray jets.
 11. A coating, comprising: acomposite material made of amorphous metal that contains the followingelements in the specified range of composition given in parentheses:manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), silicon (0.3to 3.1 atomic %), chromium (15 to 20 atomic %), molybdenum (2 to 15atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon(3 to 16 atomic %), and the balance iron.
 12. The coating of claim 11wherein said amorphous metal precipitates of yttrium oxide.
 13. Anapparatus for producing a corrosion-resistant amorphous-metal coating ona structure, comprising: a deposition chamber, a deposition source insaid deposition chamber that produces a deposition spray, saiddeposition source containing a composite material made of amorphousmetal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10atomic %), and silicon (0.3 to 3.1 atomic %) in the range of compositiongiven in parentheses; and that contains the following elements in thespecified range of composition given in parentheses: chromium (15 to 20atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %),boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balanceiron; and a system that directs said deposition spray onto thestructure, wherein said system that directs said deposition spray ontothe structure comprises a system for applying said amorphous metal tothe structure by deposition.
 14. An apparatus for producing acorrosion-resistant amorphous-metal coating on a structure, comprising:a deposition chamber, a deposition source in said deposition chamberthat produces a deposition spray, said deposition source containing acomposite material made of amorphous metal that contains manganese (1 to3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1atomic %) in the range of composition given in parentheses; and thatcontains the following elements in the specified range of compositiongiven in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon(3 to 16 atomic %), and the balance iron; and a system that directs saiddeposition spray onto the structure, wherein said system that directssaid deposition spray onto the structure comprises a system for applyingsaid amorphous metal to the structure by electrochemical deposition. 15.An apparatus for producing a corrosion-resistant amorphous-metal coatingon a structure, comprising: a deposition chamber, a deposition source insaid deposition chamber that produces a deposition spray, saiddeposition source containing a composite material made of amorphousmetal that contains manganese (1 to 3 atomic %), yttrium (0.1 to 10atomic %), and silicon (0.3 to 3.1 atomic %) in the range of compositiongiven in parentheses; and that contains the following elements in thespecified range of composition given in parentheses: chromium (15 to 20atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %),boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balanceiron; and a system that directs said deposition spray onto thestructure, wherein said system that directs said deposition spray ontothe structure comprises a system for applying said amorphous metal tothe structure by sputter deposition.
 16. An apparatus for producing acorrosion-resistant amorphous-metal coating on a structure, comprising:a deposition chamber, a deposition source in said deposition chamberthat produces a deposition spray, said deposition source containing acomposite material made of amorphous metal that contains manganese (1 to3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1atomic %) in the range of composition given in parentheses; and thatcontains the following elements in the specified range of compositiongiven in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon(3 to 16 atomic %), and the balance iron; and a system that directs saiddeposition spray onto the structure, wherein said system that directssaid deposition spray onto the structure comprises a system for applyingsaid amorphous metal to the structure by thermal spray deposition.